Carbofunctional sulfur and carboxylate bridged tin compounds

ABSTRACT

Organotin compounds are prepared having (1) at least two tin atoms linked by a bridge through sulfur, carboxylate or both and containing at least two carbon atoms in the bridge, (2) directly attached to the tin atoms one to two alkyl groups containing one to eight carbon atoms and (3) a mercaptoalkanol or derivative thereof. The compounds are useful to stabilize halogen containing vinyl and vinylidene polymers, e.g. polyvinyl chloride.

The present invention relates to novel sulfur containing organotincompounds useful as stabilizers for polyvinyl chloride and other halogencontaining polymers.

In the broadest aspect these are prepared organotin compounds having (1)at least two tin atoms linked by a bridge through sulfur, carboxylategroups or both, said bridge also containing at least two carbon atoms,(2) directly attached to the tin atoms one to two alkyl groupscontaining one to eight carbon atoms and (3) a mercaptoalkanol orderivative thereof directly attached to at least one of the tin atomsthrough the sulfur atom.

The bridges can be described as consisting of --S˜S--, ##STR1## and noother functions, e.g. there are no bis oxide, alcoholate or phenategroups in the bridge. The nature of the bridge is inconsequential solong as it contains at least two carbon atoms in the chain. Therequisite chain carbon atoms may or may not include the carboxylatecarbon atom or atoms.

The structure can thus be ##STR2## WHERE Q is --S-- or ##STR3## Z is anydivalent organic radical which together with Q contains at least twocarbon atoms, i.e. if both Q groups are --S-- then Z must have at leasttwo carbon atoms, if one Q is ##STR4## then Z must contain at least onecarbon atom and if both Q groups are ##STR5## then Z may be zero(although Z can also contain one or more carbon atoms in this casealso);

R is alkyl of 1 to 8 carbon atoms,

X IS 1 OR 2 AND THE TWO X'S CAN BE THE SAME OR DIFFERENT.

R₁ can be alkylene, arylene or substituted alkylene or arylene(preferably R₁ is unsubstituted alkylene or arylene),

Y is hydrogen, acyl, e.g. acyl of a carboxylic acid, or anything else.

In a more specific form of the invention the compounds have the formula:##STR6## where R is a monovalent alkyl radical of 1 to 8 carbon atoms, Ais ##STR7## X where X is halogen of atomic weight 35 to 127, i.e.,chlorine, bromine or iodine, ##STR8## with the proviso that at least one##STR9## is in the molecule, d is 0 or 1, each R' when d is 0 isalkylene of 1 to 10 carbon atoms; each R' when d is 1 is alkylene of 2to 10 carbon atoms, each R" when d is 1 is alkyl of 1 to 20, preferably1 to 18, carbon atoms, ethylenically unsaturated aliphatic hydrocarbylhaving 1 to 3 ethylenic double bonds and 2 to 19, preferably 2 to 17,carbon atoms, halo or hydroxy alkyl or alkenyl of 2 to 19, preferably 2to 17 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, benzyl, phenyl,halophenyl, e.g., fluorophenyl, chlorophenyl or bromophenyl,alkylphenyl, ##STR10## --R"OR"SnR_(x) where R'" is alkyl or 1 to 20,preferably 1 to 18 carbon atoms, alkenyl or 2 to 18 carbon atoms, haloor hydroxy alkyl or alkenyl or 2 to 18 carbon atoms, cycloalkyl, of 5 to6 carbon atoms, benzyl, phenyl, halophenyl, e.g., fluorophenyl,chlorophenyl or bromophenyl; R" when d is 0 is hydrogen, alkyl of 1 to20, preferably 1 to 18 carbon atoms, ethylenically unsaturated aliphatichydrocarbyl having 1 to 3 ethylenic double bonds and 2 to 19, preferably2 to 18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, benzyl, phenylor halophenyl, e.g., fluorophenyl, bromophenyl or chlorophenyl, x is 1or 2, y is 1 or 2 and z is 1 or 2, the total of x+y+z is 4, preferably xand z are 1 and y is 2, secondarily x is 2 and y and z are 1, ##STR11##where R₄ is alkylene of 2 to 10 carbon atoms, --CH═CH--, arylene(preferably phenylene, ##STR12## n is 1 or 2, R₅ is nothing, phenylene(e.g. from terephthalic acid), alkylene of 1 to 8 carbon atoms or--CH═CH--, R₆ is alkylene of 1 to 10 carbon atoms, --CH═CH--, arylene(preferably phenylene) or, R₈ is a residue of a diol, e.g. atoms theresidue of a glycol such as alkylene of 2 to 10 carbon atoms,cyclohexane dimethylene, etc., R₉ is a residue of a dicarboxylic acid,e.g. --(CH₂) where m is an integer from 0 to 8, --CH═CH--, or phenylene,(particularly here the free bonds are in the para position), R₁₀ isarylene, e.g. phenylene or ##STR13## where t is 0 to 1 and R₁₁ and R₁₂are hydrogen or alkyl, preferably t is 1 and R₁₁ and R₁₂ are bothmethyl, and compounds prepared by reacting a dialkyltin oxide or alkylstannoic acid with a compound of the formula. ##STR14##

The grouping ##STR15## can be formed by reacting two moles ofmercaptoethanol and one mole of maleic acid. The grouping ##STR16## canbe formed by reacting two moles of thioglycolic acid or betathiopropionic acid with one mole of a diol, e.g. ethylene glycol,diethylene glycol, propylene glycol, decamethylene glycol. The grouping##STR17## can be formed by reacting two moles of a dicarboxylic acid,e.g. maleic acid, oxalic acid, succinic acid, adipic acid, terephthalicacid with one mole of a dihydric phenol, e.g. hydroquinone or abisphenol, e.g. 4,4'-dihydroxydiphenyl, p,p'-diphenylolpropane(bisphenol A), bis (4-hydroxyphenyl) methane, etc.

The compounds are useful to stabilize halogen containing vinyl andvinylidene resins, e.g. polyvinyl chloride.

Examples of groups within R are methyl, ethyl, propyl, isopropyl,n-butyl, isobutyl, sec. butyl, t-butyl, amyl, hexyl, octyl, 2-ethylhexyland isoctyl. Most preferably R is methyl. Examples of subgroups within Rare (a) methyl and butyl and (b) methyl, butyl and octyl.

When A is halogen it is preferably chlorine.

Examples of R' (and also of R₆) groups are methylene, ethylene,propylene, trimethylene, tetramethylene, pentamethylene, octamethylene,hexamethylene, decamethylene, p-phenylene and m-phenylene. Examples ofR₄ are the same as those mentioned for R' except that methylene isomitted. Examples of R₅ are nothing, methylene, ethylene, trimethylene,propylene, tetramethylene, pentamethylene, hexamethylene, octamethylene,--CH═CH-- (either cis or trans).

The compounds of the present invention can be made in various ways suchas those illustrated below, for example.

Conveniently, the tin is added as the monoalkyltin trihalide, e.g.,methyltin trichloride, methyltin tribromide, methyltin triiodide,ethyltin trichloride, sec. butyltin trichloride, butyltin tribromide oroctyltin trichloride, the dialkyltin dihalide, e.g., dimethyltindichloride, dimethyltin dibromide, dimethyltin diiodide, dipropyltindichloride.

When monomethyltin and dimethyltin halides or other mono or dimethyltinstarting compounds are used in order to insure low toxicity, the amountof tin present as trimethyltin compound impurity should be less than0.5%.

The ##STR18## grouping can be attached to the tin by reacting the abovementioned mono or dialkyltin halides with a compound having the formula##STR19## Thus there can be employed mercaptoalkanol esters, forexample, esters of mercaptoethanol, 2-thioglycerine, 3-thioglycerine,3-thiopropanol, 2-thiopropanol, 4-thiobutanol, 18-thio-octadecanol,9-thiononanol, 8-thiooctanol, 6-thiohexanol with acids such as formicacid, acetic acid, propionic acid, butyric acid, pivalic acid, valericacid, caprylic acid, caproic acid, decanoic acid, lauric acid, myristicacid, palmitic acid, 2-ethylhexanoic acid, stearic acid, eicosanic acid,oleic acid, linoleic acid, linolenic acid, crotonic acid, methacrylicacid, acrylic acid, cinnamic acid, benzoic acid, p-toluic acid, o-toluicacid, p-t-butyl-benzoic acid, enanthic acid, p-n-butylbenzoic acid,cyclohexane carboxylic acid, phenylacetic acid, ricinoleic acid,hydrogenated ricinoleic acid, phenylpropionic acid. Of course, mixturesof acids can be used, e.g., tall oil acids, palmitic acid-stearic acidmixtures ranging from 60:40 to 40:60; soybean oil acids, cottonseed oilacids, hydrogenated cottonseed oil acids, peanut oil acids, coconut oilacids, corn oil acids, castor oil acids, hydrogenated castor oil acids,lard acids, etc. Illustrative of half esters of polycarboxylic acidswhich can be esterified with the mercaptoalkanol are mono methylmaleate, monoethyl maleate, monopropyl maleate, monobutyl maleate,monooctyl maleate, mono-2-ethylhexyl maleate, mono stearyl maleate,monoethyl fumarate, monomethyl oxalate, monoethyl oxalate, monoethylmalonate, monobutyl malonate, monoisopropyl succinate, monomethylsuccinate, monomethyl glutarate, monoethyl adipate, monomethyl azelate,monomethyl phthalate, monoethyl phthalate, mono-isooctyl phthalate,monoethyl terephthalate.

Illustrative of mercapto esters which can be used for reaction with thetin compound are:

2-mercaptoethyl acetate,

2-mercaptoethyl propionate,

2-mercaptoethyl butyrate,

2-mercaptoethyl valerate,

2-mercaptoethyl pivalate,

2-mercaptoethyl caproate,

2-mercaptoethyl caprylate,

.[.2pelargonate, pelargonte.]. .Iadd.2-mercaptoethylpelargonate.Iaddend. ,

2-mercaptoethyl decanoate,

2-mercaptoethyl laurate,

2-mercaptoethyl stearate,

2-mercaptoethyl eicosanate,

2-mercaptoethyl palmitate,

2-mercaptoethyl oleate,

2-mercaptoethyl ricinoleate,

2-mercaptoethyl linoleate,

2-mercaptoethyl linolenate,

2-mercaptoethyl tallate,

2-mercaptoethyl ester of cottonseed oil acid,

2-mercaptoethyl ester of lard acids,

2-mercaptoethyl ester of coconut oil acids,

2-mercaptoethyl ester of soybean oil acids,

2-mercaptoethyl benzoate,

2-mercaptoethyl p-toluate,

2-mercaptoethyl crotonate,

2-mercaptoethyl cinnamte,

2-mercaptoethyl phenyl acetate,

2-mercaptoethyl phenyl propionate,

2-mercaptoethyl methyl maleate,

2-mercaptoethyl ethyl fumarate,

2-mercaptoethyl butyl oxalate,

2-mercaptoethyl methyl oxalate,

2-mercaptoethyl ethyl malonate,

2-mercaptoethyl methyl succinate,

2-mercaptoethyl methyl azelate,

2-mercaptoethyl hexyl azelate,

2-mercaptoethyl methyl phthalate,

3-mercaptopropyl pelargonate,

3-mercaptopropyl enanthate,

3-mercaptopropyl stearate,

3-mercaptopropyl oleate,

3-mercaptopropyl ricinoleate,

3-mercaptopropyl ethyl maleate,

3-mercaptopropyl benzoate,

2-thioglyceryl pelargonate,

3-thioglyceryl pelargonate, 2-mercaptoethyl-bromoacetate,

6-mercaptohexyl acetate, 2-mercaptoethyl-3'-fluorobenzoate,

7-mercaptoheptyl acetate, 2-mercaptoethyl-2'-bromobenzoate,

7-mercaptoheptyl propionate, 2-mercaptoethyl-4'-chlorobenzoate,

8-mercaptooctyl acetate, 2-mercaptoethyl-2'-chloropropionate,

8-mercaptooctyl enanthate, 2-mercaptoethyl chloroacetate,

18-mercaptooctadecyl acetate, 2-mercaptoethyl trichloroacetate,

18-mercaptooctadecyl enanthate, 2-mercaptoethyl cylohexanoate,

2-mercaptoethyl cyclopentanoate.

When d is zero sulfur compounds employed include thioalkanols such as2-mercaptoethanol, 3-mercapto-propanol, 4-mercaptobutanol,3-mercaptobutanol, 5-mercaptopentanol, 10-mercaptodecanol.

Additional starting compounds of the formula ##STR20## includemonothioglycerine dicaprylate, monothioglycerine diacetate,monothioglycerine distearate, monothioglycerine dioleate,monothioglycerine dilinoleate.

The Z linkage in the compounds except when Z is --O-- can be formed byreacting a compound of the formula HZH with a compound of the formula:##STR21## where Hal is a halogen, e.g., chlorine, bromide or iodine.Examples of compounds having the formula HZH aremercaptoethylmercaptopropionate, mercaptoethylthioglycolate,3-mercaptopropylthioglycolate, 3-mercaptopropyl mercaptopropionate,mercaptoethylmercapto-butyrate, mercaptoethyl mercaptodecanoate,10-mercaptodecylthioglycolate, 4-mercaptobutylmercaptopropionate,mercaptoethylthioglycolic acid mercaptoethyl ester,mercaptopropyl-thioglycolic acid mercaptoethyl ester,mercaptoethylthioglycolic acid, mercaptopropyl ester,mercaptoethylmercaptopropionic acid mercaptoethyl ester,mercaptopropylmercaptopropionic acid mercaptopropyl ester,bis(2-mercaptoethyl) adipate, bis(3-mercaptopropyl adipate)bis(4-mercaptobutyl)adipate, bis(10-mercapto-decyl)adipate,bis(2-mercaptoethyl)maleate, bis(3-mercaptopropyl)maleate,bis(2-mercaptopropyl)adipate, bis(4-mercaptobutyl)maleate,bis(2-mercaptoethyl)furmarate, bis(3-mercaptopropyl)fumarate,bis(2-mercaptoethyl)oxalate, bis(3-mercaptopropyl)malonate,bis(2-mercaptoethyl)succinate, bis(3-mercaptopropyl) succinte,bis(2-mercaptoethyl) glutarate, bis(3-mercaptopropyl) azelate,bis(2-mercaptoethyl) suberate, bis(2-mercaptoethyl) sebacate,bis(2-mercaptoethyl) terephthalate, thioglycolic acid, alpha mercaptopropionic acid, beta mercaptopropionic acid, alpha mercaptobutyric acid,gamma mercaptobutyric acid, oxalic acid, malonic acid, adipic acid,succinic acid glutaric acid, azelaic acid, sebacic acid, ethanedithiol,propanedithiol-1,3, butanedithiol-1,4, butanedithiol-1,3hexanedithiol-1,6, decanedithiol-1,10, mercaptoethanol,3-mercaptopropanol, 4-mercaptobutanol, mono-mercaptoethyl maleate,mono-mercaptoethyl fumarate, mono-mercaptoethyl adipate,monomercaptopropyl adipate, mono-mercaptoethyl terephthalate,bis(2-mercaptoethyl) maleate, mono-mercaptoethyl, sebacate,mono-mercaptoethyl succinate, tetramethylene glycol bis maleate,tetramethylene glycol bis fumarate, tetramethylene glycol bis succinate,tetramethylene glycol bis sebacate, tetramethylene glycol bis oxalate,ethylene glycol bis terepthalate, tetramethylene glycolbis(mercaptoacetate), ethylene glycol bis maleate, ethylene glycol bisfumarate, propylene glycol bis(3-mercaptopropionate), bisphenol Abis(maleate), ethylene glycol bis adipate, ethyleneglycol bis glutarate,bisphenol A bis(terepthalate), bisphenol A bis(adipate), propyleneglycol bis maleate, propylene glycol bis adipate, trimethylene glycolbis adipate, hexamethylene glycol bis adipate, hexamethylene glycol bismaleate, decamethylene glycol bis adipate, decamethylene glycol bismaleate.

When Z is --O-- the products of the invention can be prepared byreacting either an alkyl halotin dihydroxide, e.g., methyl chlorotindihydroxide, butyl chlorotin dihydroxide, octylchlorotin dihydroxide,methyl bromotin dihydroxide or an alkyl stannoic acid, e.g., methylstannoic acid, butylstannoic acid, octylstannoic acid with a compound ofthe formula: ##STR22## In addition to the group of compounds set forthabove, there can also be employed overbased tin compounds by reacting adialkyltin oxide of the formula ##STR23## dimethyltin oxide, dibutyltinoxide, or dioctyltin oxide, or an alkylstannoic acid RSnOOH, e.g.,methylstannoic acid, butylstannoic acid or octylstannoic acid with acompound of the invention of the formula: ##STR24## There can be used upto 2 moles, e.g., 0.1 to 2 moles of dialkyltin oxide or alkylstannoicacid per ester group of the sulfur containing compounds.

The overbased product has the same uses as the other products of theinvention. It is particularly surprising that overbased products can bemade with dimethyltin oxide since while it is not soluble in many othermaterials, it is soluble in the compounds of the invention.

The overbasing reaction is further shown in Weisfeld U.S. Pat. No.3,478,071 and Stapfer et al, J. Organometallic Chemistry Vol. 24 (1970)pages 355-358. The entire disclosures of the Weisfeld patent and Stapferarticle are hereby incorporated by reference.

In preparing the compounds of the invention, various processes can beemployed some of which are illustrated in the working examples.Regardless, however, of the method employed, the reaction can be carriedout at a wide range of temperatures, e.g., room temperature to 100° C.usually at 25° - 50° C. The reaction is usually carried out with wateras a solvent, regardless of the procedure employed. There can also beemployed water immiscible organic solvents, e.g., aliphatic and aromatichydrocarbons, e.g., hexane, octane, benzene, toluene, xylene, aliphaticcarboxylic Acid esters, e.g., butyl acetate, propyl propionate, methylvalerate. The proportions of solvent are not critical and can varywidely.

Unless otherwise indicated, all parts and percentages are by weight.

In the examples, the refractive indices (R.I.) were measured at 25° C.unless otherwise indicated.

EXAMPLE 1

Into a 3-necked flask is placed 120 gm (0.5 mole) ofmethyltintrichloride dissolved in 200 ml of water. The mixture is armedto 30° C. and there is added 204 gm (1.0 mole) of 2-mercaptoethylcaprylate. Then there is added dropwise at 30° C. 80 gm (1.0 mole) of50% aqueous sodium hydroxide. The mixture is stirred for 1 hour at30°-40° C. After this reaction time, 66.5 gm (0.25 mole) ofbis(2-mercaptoethyl) adipate is added portionwise followed by 40 g (0.5mole) of 50% NaOH and the mixture allowed to stir 1 hour at 30°-40° C.The product layer is separated and washed with 200 ml of water. Theproduct is then stripped under vacuum to 100° C. resulting in 318 gm. ofa nearly colorless oil. The product is mainly bis(methyltinbis[2-mercaptoethyl caprylate]-mercaptoethyl)adipate.Iadd. , n_(D) ²⁵1.5283 .Iaddend.

EXAMPLE 2

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 42 gm (0.25 mole) ofmercaptoethylmercaptopropionate. Obtained is 295 gm of a pale yellowoil, bis(methyltinbis[2-mercaptoethylcaprylate])mercaptoethylmercaptopropionate, .[.D²⁵.]. .Iadd.n_(D) ²⁵ .Iaddend. 1.5352.

EXAMPLE 3

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 59 gm (0.25 mole) ofbis(2-mercaptoethyl)maleate. Obtained is 302 gm of a pale yellow oil,bis(methyl-tin bis[2-mercaptoethylcaprylate]mercaptoethyl) maleate.n_(D) ²⁵ 1.5389.

EXAMPLE 4

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 52 gm (0.25 mole) of glycolbis(thioglycolate). Obtained is 299 gms of a nearly colorless oil, n_(D)²⁵ 1.5193. The product includes: ##STR25##

EXAMPLE 5

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 23 gm (0.25 mole of thioglycolic acid.Obtained is 273 gms of a colorless oil n_(D) ²⁵ 1.5404. The productincludes: ##STR26##

EXAMPLE 6

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 29 gm (0.25 mole) of maleic acid.Obtained is 276 gm of yellow oil. n_(D) ²⁵ 1.5371. The product includes:##STR27##

EXAMPLE 7

Into a 3-necked flask is placed 120 g (0.5 mole) of methyltintrichloridedissolved in 200 ml of water. The mixture is warmed to 30° C. and thereis added 153 gm (0.75 mole) of 2-mercaptoethylcaprylate. Then there isadded dropwise at 30° C., 60 gms (0.75 mole) of 50% aqueous sodiumhydroxide. The mixture is stirred for 1 hour at 30°-40° C. After thisreaction time 66.5 gm (0.25 mole) of bis(2-mercaptoethyl) adipate isadded portionwise followed by 40 gm (0.50 mole) of 50% aqueous NaOH, andthe mixture allowed to stir 1 hour at 30°-40° C. The product layer isseparated and washed with 200 ml of water. The product is then strippedunder reduced pressure resulting in 263 gms of colorless oil. n_(D) ²⁵1.5396. The product includes: ##STR28##

EXAMPLE 8

Into a 3-necked flask is placed 110 gm (0.5 mole) of dimethyltindichloride dissolved in 200 ml of water. The mixture is warmed to 30° C.and there is added 170 gm (0.5 mole) 2-mercaptoethyloleate. Then thereis added dropwise at 30° C. 40 gms (0.5 mole) of 50% aqueous sodiumhydroxide. The mixture is stirred for 1 hour at 30°-40° C. After thisreaction time, 66.5 gm (0.25 mole) of bis(2-mercaptoethyl) adipate isadded, then followed closely by 40 gm (0.5 mole) of 50% aqueous NaOHthen allowed to stir 1 hour at 30°-40° C. The product layer is separatedand washed with 200 ml of water, then stripped under vacuum to 100° C.,resulting in 296 gm of a yellow oil. n_(D) ²⁵ 1.5106. The reactionproduct contains: ##STR29##

EXAMPLE 9

Into a 3-necked flask is placed 55 gms (0.25 mole)dimethyltindichloride, 60 gm (0.25 mole) of methyltin trichloridedissolved in 200 ml of water. The mixture is warmed to 30° C. and thereis added 255 (0.75 mole) of 2-mercaptoethyloleate. .[.Then there isadded dropwise at 30° C. 60 gm (0.75 mole) of 2-mercaptoethyloleate..].Then there is added dropwise at 30° C. 60 gm (0.75 mole) of 50% aqueoussodium hydroxide. The mixture is stirred for 1 hour at 30°-40° C. Afterthis reaction time, 66.5 gm (0.25 mole) of bis(2-mercaptoethyl)adipateis added, then followed immediately by 40 gm (0.50 mole) of aqueousNaOH, then allowed to stir 1 hour at 30°-40° C. The product layer isseparated, washed with 200 ml of water, then stripped under vacuum to100° C. resulting in 383 gm of a yellow oil. n_(D) ²⁵ 1.5080. Thereaction product contains: ##STR30##

EXAMPLE 10

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 41.5 gm (0.25 mole) 2-mercaptoethylmaleate. Obtained are 287 gms of a pale yellow oil, n_(D) ²⁵ 1.5384. Theproduct includes: ##STR31##

EXAMPLE 11

The procedure of Example 1 was followed replacing the2-mercaptoethylcaprylate with 330 gm (1.0 mole) of2-mercaptoethyloctadecylether. Obtained is 441 gm of a nearly colorlessoil, containing bis(methyltinbis[2-mercaptoethyloctadecylether]-mercaptoethyl)adipate. n_(D) ²⁵1.5149.

EXAMPLE 12

The procedure of Example 1 as followed replacing the2-mercaptoethylcaprylate with 360 gm (0.0 mole) of monothioglycerinedicaprylate ester. Obtained is 458 gm of a yellow oil, containingbis(methyltin bis[thioglycerinedicaprylate]-2-mercapto-ethyl)adipate.n_(D) ²⁵ 1.5160.

EXAMPLE 13

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 23.5 gm (0.25 mole) ethanedithiol.Obtained is 269 mg of a very odoriferous pale yellow oil, n_(D) ²⁵1.5272 containing: ##STR32##

EXAMPLE 14

The procedure of Example 1 was followed replacing the2-mercaptoethylcaprylate with 260 gm (1.0 mole) of6-mercaptohexylcaprylate. Obtained is 366 gm of a pale yellow oil, n_(D)²⁵ 1.5202, mainly bis(methyltinbis[6-mercaptohexylcaprylate]-2-mercaptoethyl)adipate.

EXAMPLE 15

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl)adipate with 71.5 gm (0.25 mole) of tetramethyleneglycol bis maleate. Obtained is 314 gm of a pale yellow oil. n_(D) ²⁵1.5349, containing ##STR33##

EXAMPLE 16

The procedure of Example 9 was followed replacing thebis(2-mercaptoethyl)adipate with 38 gm (0.25 mole) ofmercaptoethylthioglycolate. Obtained is 342 gm of a pale yellow oil,n_(D) ²⁵ 1.5161, containing: ##STR34##

EXAMPLE 17

Into a 3-necked flask is placed 55 gm (0.25 mole) dimethyltindichloride,60 gm (0.25 mole) methyltintrichloride dissolved in 200 ml of water. Themixture is warmed to 30° C. and there is added 102 gm (0.50 mole) of2-mercaptoethyl caprylate. Then there is added dropwise at 30° C. 40 gm(0.5 mole) of 50% aqueous sodium hydroxide. The mixture is stirred for 1hour at 30°-40° C. After this reaction time 42 gm (0.25 mole) ofmercaptoethylmercaptopropionate is added, then followed immediately by40 gm (0.5 mole) aqueous NaOH (50%), then allowed to stir 1 hour at30°-40° C. The product layer is separated washed with 200 ml of water,then stripped under vacuum to 100° C. resulting in 192 gm of a yellowoil n_(D) ²⁵ 1.5428 containing: ##STR35##

EXAMPLE 18

The procedure of Example 1 was followed replacing themonomethyltintrichloride with 141 gm (0.5 mole) of butyltintrichloride.Obtained is 330 gm of a pale yellow oil. The product is mainlybis(butyltin bis[2-mercaptoethyl caprylate]-2-mercaptoethyl)-adipate,n_(D) ²⁵ 1.5210.

EXAMPLE 19

The procedure of Example 7 was followed replacing themethyltintrichloride with 141 gm (0.5 mole) of butyltintrichloride andthe bis(2-mercaptoethyl)adipate with 59 gm (0.25 mole) ofbis(2-mercaptoethyl)-maleate. Obtained is 280 gm of a nearly colorlessoil, n_(D) ²⁵ 1.5420, containing: ##STR36##

EXAMPLE 20

The procedure of Example 9 was followed, replacing thedimethyltindichloride with 75.5 gm (0.25 mole) of dibutyltindichloride,the methyltintrichloride with 70.5 gm (0.25 mole) ofbutyltintrichloride. Obtained is 402 gms of a yellow oil, n_(D) ²⁵1.5077, containing: ##STR37##

EXAMPLE 21

Into a 3-necked flask is placed 329 gm (0.25 mole) of bis(methyltinbis[2-mercaptoethyl caprylate]mercaptoethyl) adipate and 41 gm (0.25mole) of dimethyltin oxide. The mixture is heated at 80°-120° C. over a2-hour period, cooled to 40°-50° C. and filtered yielding 370 gms of apale yellow oil n_(D) ²⁵ 1.5303 containing: ##STR38## where the Me₂ SnOis inserted into one of the ester functions, possibly ##STR39##

EXAMPLE 22

Into a 3-necked flask is placed 122.5 gm (0.5 mole) of"butylchlorotindihydroxide," 165 gm (0.5 mole) of 2-mercaptoethyl oleateand 750 ml of toluene. The mixture is refluxed until 8.5 ml of water areremoved. The organic layer is stripped yielding 260 gm of a yellow oil.n_(D) ²⁵ 1.5320. The oil containsbis(monobutylmonochlorotin[2-mercaptoethyloleate]) oxide.

EXAMPLE 23

Into a 3-necked flask is placed 113.5 gm (0.5 mole) of butylstannoicacid, 204 gm (1.0 mole) of 2-mercaptoethylcaprylate and 300 ml oftoluene. The mixture is refluxed until 18.0 ml of water are removed. Theorganic layer is stripped yielding 290 gm of a nearly colorless oil,n_(D) ²⁵ 1.5232. The oil contains bis(monobutyltinbis[2-mercaptoethylcaprylate].sup..[.D.].) oxide.

EXAMPLE 24

The procedure of Example 1 was followed replacing thebis(2-mercaptoethyl) adipate with 41.5 g (0.25 mole) of terephthalicacid. Obtained is 286 gm of yellow oil. n_(D) ²⁵ 1.5488. The product isin part ##STR40##

EXAMPLE 25

The procedure of Example 9 was followed replacing thebis(2-mercaptoethyl) adipate with 105 g (0.25 mole) of reaction productof bis phenol A 118 gms (0.5 mole) and 116 gms (1.0 mole) maleic acid.Obtained is 421 gm of amber oil. n_(D) ²⁵ 1.5286. The reaction productcontains ##STR41##

The stabilizers of the present invention can be used withhalogen-containing vinyl and vinylidene polymers, e.g., resins in whichthe halogen is attached directly to the carbon atoms. Preferably thepolymer is a vinyl halide polymer, specifically a vinyl chloridepolymer. Usually, the vinyl chloride polymer is made from monomersconsisting of vinyl chloride alone or a mixture of monomers comprisingat least 70% vinyl chloride by weight. When vinyl chloride copolymersare stabilized, preferably the copolymer of vinyl chloride with anethylenically unsaturated compound copolymerizable therewith contains atleast 10% of polymerized vinyl chloride.

As the chlorinated polymer there can be employed chlorinatedpolyethylene having 14 to 75%, e.g., 27% chloride by weight, chlorinatednatural and synthetic rubber, rubber hydrochloride, chlorinatedpolystyrene, chlorinated polyvinyl chloride, polyvinyl chloride,polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride,copolymers of vinyl chloride with 1 to 90%, preferably 1 to 30% of acopolymerizable ethylenically unsaturated material such as vinylacetate, vinyl butyrate, vinyl benzoate, vinylidene, chloride, diethylfumarate, diethyl maleate, other alkyl fumarates and maleates, vinylpropionate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate andother alkyl acrylates, methyl methacrylate, ethyl methacrylate, butylmethacrylate and other alkyl methacrylates, methyl alpha chloroacrylate,styrene, trichloroethylene, vinyl ethers such as vinyl ethyl ether,vinyl chloroethyl ether and vinyl phenyl ether, vinyl ketones such asvinyl methyl ketone and vinyl phenyl ketone, 1-fluoro-2-chloroethylene,acrylonitrile, chloroacrylonitrile, allylidene diacetate andchloroallyidene diacetate. Typical copolymers include vinylchloride-vinyl acetate (96:4 sold commercially as VYNW), vinylchloride-vinylacetate (87:13), vinyl chloride-vinyl acetate-maleicanhydride (86:13:1), vinyl chloride-vinylidene chloride (95:5), vinylchloride-diethyl fumarate (95:5), vinyl chloride-trichloroethylene(95:5), vinyl chloride-2-ethylhexyl acrylate (80:20).

The stabilizers of the present invention can be incorporated with thepolymer by admixing in an appropriate mill or mixer of by any of theother well-known methods which provide for uniform distributionthroughout the polymer composition. Thus, mixing can be accomplished bymilling on rolls at 100°-160° C.

In addition to the novel stabilizers, there can also be incorporatedwith the resin, conventional additives such as plasticizers, pigments,fillers, dyes, ultraviolet light absorbing agents, densifying agents andthe like. There can also be added conventional and known tinstabilizers, e.g., those disclosed in Kauder or Kugele et al or inWeisfeld U.S. Pat. No. 3,640,950, Leistner U.S. Pat. Nos. 2,870,119 and2,870,182, Best U.S. Pat. No. 2,731,484, Stefl U.S. Pat. No. 2,731,482,and Mack U.S. Pat. No. 2,914,506, for example. The entire disclosures ofall the patents mentioned in this paragraph are hereby incorporated byreference.

If the plasticizer is employed, it is used in conventional amount, e.g.,10 to 150 parts per 100 parts of polymer. Typical plasticizers aredi-2-ethylhexyl phthalate, dibutyl sebacate, dioctyl sebacate, tricresylphosphate.

The tin containing stabilizers of the invention are normally used in anamount of 0.01 to 10% by weight of the polymer, more preferably 0.2 to5% of the tin compound is used by weight of the polymer.

As indicated, there can also be incorporated 0.1 to 10 parts per 100parts of the halogen containing polymer of a metal salt stabilizer.Thus, there can be used barium, strontium, calcium, cadmium, zinc, lead,tin, magnesium, cobalt, nickel, titanium and aluminum salts of phenols,aromatic carboxylic acids, fatty acids or epoxy fatty acids.

Examples of suitable salts include barium di(nonylphenolate), strontiumdi(nonylphenolate), strontium di(amylphenolate), bariumdi(octylphenolate), strontium di(octylphenolate), bariumdi(nonyl-o-cresolate), lead di(octylphenolate), cadmium-2-ethyl hexoate,cadmium laurate, cadmium stearate, zinc caprylate, cadmium caprate,barium stearate, barium-2-ethylhexoate, barium laurate, bariumricinoleate, lead stearate, aluminum stearate, magnesium stearate,calcium octoate, calcium stearate, cadmium naphthenate, cadmiumbenzoate, cadmium p-tert. butylbenzoate, barium octyl salicylate,cadmium epoxy stearate, strontium epoxy stearate, cadmium salt ofepoxidized acids of soybean oil, and lead epoxy stearate.

In plastisol formulations there is preferably also included from 0.1 to10 parts per 100 parts of polymer of an epoxy vegetable oil such asepoxidized soybean oil or epoxidized tall oil, epoxy esters of fattyacids, e.g., isooctyl epoxystearate.

EXAMPLE 26

100 Parts of a polyvinyl chloride commercially available under the tradedesignation Geon 103 EP are admixed with 1.0 parts Omya 90T (fineparticle size CaCO₃ coated with Ca stearate), 1.0 part of a paraffin waxcommercially available under the trade designation Advawax 165, 0.1 partAC 629A (oxidized low molecular weight ethylene homopolymer) andstabilizer as noted in Table I. The composition is heated to 380° F. andmilled with sampling at 1 minute intervals after first introduction ofmixture to the mill. The results of the tests are found in Table I.

                                      TABLE 1                                     __________________________________________________________________________                   Dynamic Mill Stability                                         Product of                                                                           Tin Contained                                                                         380° F. 30/40 RPM(minutes)                              Example No.                                                                          (mg)    1  2   3  4  5  6  7  8 9 10                                   __________________________________________________________________________    1      40      10 10  9  7+ 6  5  4  2 2 2                                    2      40      10 9+  9  8  6  5  4  3 1 1                                    3      40      10+                                                                              10+ 10 9  8  7+ 5  3 2 2                                    5      40      9  8   7  5  4  3  3  2 2 1                                    7      40      9  8+  8  7  6  5  4  3 2 1                                    8      40      8+ 8   7  6  5  4  4  3 2 2                                    9      40      10 10  9+ 8+ 7  6  5+ 4 3 2                                    *      40      9  8   7  6  5  5  4  2 2 2                                    __________________________________________________________________________     Color Scale:                                                                  *2/3 monomethyltin tris(isooctylthioglycolate) and 2/3 dimethyltin            bis(isooctylthioglycolate)                                               

As can be seen from Table I the products of the invention on the wholeshowed as good or better dynamic mill stability than the comparativestabilizer.

What is claimed is:
 1. A sulfur containing organotin compound having theformula (1): ##STR42## where R is a monovalent alkyl radical of 1 to 8carbon atoms, A is ##STR43## halogen of atomic weight 35 to 127.##STR44## the A groups are the same or different with the proviso thatat least one ##STR45## is in the molecule, d is 0 or 1, each R' when dis 0 is alkylene of 1 to 10 carbon atoms, each R' when d is 1 isalkylene of 2 to 10 carbon atoms, each R" .Iadd.when d is 1 .Iaddend.is.[.hydrogen,.]. alkyl of 1 to 20 carbon atoms, ethylenically unsaturatedaliphatic hydrocarbyl having 1 to 3 ethylenic double bonds and 2 to 19carbon atoms, halo or hydroxy alkyl of 2 to 19 carbon atoms, halo orhydroxy alkenyl of 2 to 19 .Iadd.carbon atoms.Iaddend., cycloalkyl of 5to 6 carbon atoms, benzyl, phenyl, alkylphenyl, halophenyl, ##STR46##where R'" is alkylene of 2 to 10 carbon atoms, .Iadd.each R" when d is 0is hydrogen, alkyl of 1 to 20 carbon atoms, ethylenically unsaturaedaliphatic hydrocarbyl having 1 to 3 ethylenic double bonds and 2 to 19carbon atoms, cycloalkyl of 5 to 6 carbon atoms, benzyl, phenyl orhalophenyl, .Iaddend.R"" is alkyl of 1 to 20 carbon atoms, alkenyl of 2to 18 carbon atoms, halo or hydroxy alkyl of 2 to 20 carbon atoms, haloor hydroxy alkenyl of 2 to 20 carbon atoms, cycloalkyl of 5 to 6 carbonatoms, benzyl, phenyl or halophenyl, x is 1 or 2, y is 1 or 2 and z is 1or 2, the total of x+y+z is 4, ##STR47## where R₄ is arylene, --CH═CH--,alkylene of 2 to 10 carbon atoms, R₅ is nothing, alkylene of 1 to 8carbon atoms, phenylene or --CH═CH--, R₆ is alkylene of 1 to 10 carbonatoms, --CH═CH-- or arylene, R₉ is a residue of a dicarboxylic acid fromwhich the two carboxyl groups have been removed, R₁₀ is arylene or##STR48## where t is 0 to 1 and R₁₁ and R₁₂ are H or alkyl, or (2) anoverbased compound prepared by reacting a dialkyltin oxide ofalkystannoic acid with a compound of the formula: ##STR49##
 2. Acompound according to claim 1 having formula (1).
 3. A compoundaccording to claim 2 wherein x and z are 1 and y is
 2. 4. A compoundaccording to claim 3 wherein one A attached to each tin atom is halogenof atomic weight 35 to 127, and the other A is ##STR50##
 5. A compoundaccording to claim 3 wherein all of the A groups are ##STR51##
 6. Acompound according to claim 2 wherein d is
 0. 7. A compound according toclaim 6 wherein x and z are 1 and y is
 2. 8. A compound according toclaim 2 wherein, z is 1 and the A groups are ##STR52## or halogen ofatomic weight 35 to
 127. 9. A compound according to claim 8 wherein Z is##STR53##
 10. A compound according to claim 9 wherein R" is alkyl orethylenically unsaturated aliphatic hydrocarbyl.
 11. A compoundaccording to claim 10 wherein R₄ is alkylene.
 12. A compound accordingto claim 10 wherein R₄ is p-phenylene.
 13. A compound according to claim10 wherein R₄ is --CH═CH--.
 14. A compound according to claim 8 whereinZ is ##STR54##
 15. A compound according to claim 14 wherein R₄ and R₆are both alkylene.
 16. A compound according to claim 14 wherein R₄ andR₆ are both --CH═CH--.
 17. A compound according to claim 14 where R₄ andR₆ are both ##STR55##
 18. A compound according to claim 14 wherein R" isalkyl or ethylenically unsaturated aliphatic hydrocarbyl.
 19. A compoundaccording to claim 8 wherein Z is ##STR56##
 20. A compound according toclaim 8 wherein Z is ##STR57##
 21. A compound according to claim 20wherein R" is alkyl or ethylenically unsaturated aliphatic hydrocarbyl.22. A compound according to claim 8 where Z is ##STR58##
 23. A compoundaccording to claim 22 wherein R" is alkyl or ethylenically unsaturatedaliphatic hydrocarbyl.
 24. A compound according to claim 23 wherein R₅is nothing or alkylene.
 25. A compound according to claim 23 wherein R₅is --CH═CH--.
 26. A compound according to claim 23 wherein R₅ isphenylene.
 27. A compound according to claim 8 wherein Z is ##STR59##28. A compound according to claim 27 wherein R" is alkyl orethylenically unsaturated aliphatic hydrocarbyl.
 29. A compoundaccording to claim 8 wherein Z is ##STR60##
 30. A compound according toclaim 29 wherein R" is alkyl or ethylenically unsaturated aliphatichydrocarbyl.
 31. A compound according to claim 8 wherein Z is ##STR61##32. A compound according to claim 31 wherein R" is alkyl orethylenically unsaturated aliphatic hydrocarbyl.
 33. A compoundaccording to claim 8 wherein Z is ##STR62##
 34. A compound according toclaim 33 wherein n is
 2. 35. A compound according to claim 8 wherein Zis ##STR63##
 36. A compound according to claim 35 where n is
 1. 37. Acompound according to claim 35 wherein R₈ is alkylene of 2 to 10 carbonatoms.
 38. A compound according to claim 8 wherein Z is ##STR64##
 39. Acompound according to claim 38 wherein R₉ is (CH₂)_(m) where m is aninteger from 0 to
 8. 40. A compound according to claim 38 wherein R₉ is--CH═CH--.
 41. A compound according to claim 38 wherein R₉ is ##STR65##42. A compound according to claim 38 where R₁₀ is ##STR66##
 43. Acompound according to claim .[.2.]. .Iadd.42 .Iaddend.wherein R₁₁ andR₁₂ are methyl.
 44. A compound according to claim 43 wherein R₉ is(CH₂)_(m) where m is an integer of 0 to 8, --CH═CH-- or phenylene.
 45. Acompound according to claim 2 wherein d is 1 and R" is alkyl,ethylenically unsaturated aliphatic hydrocarbyl or monohydroxysubstituted monoethylenically unsaturated aliphatic hydrocarbyl.
 46. Acompound according to claim 45 wherein at least one of the A groups is##STR67## and the balance of the A groups are ##STR68## or halogen ofatomic weight 35 to
 127. 47. A compound according to claim 46 whereinall of the A groups are ##STR69##
 48. A compound according to claim 46wherein at least one A group is halogen of atomic weight 35 to
 127. 49.A compound according to claim 48 wherein the halogen is chlorine.
 50. Acompound according to claim 1 which is (2).
 51. A compound according toclaim 50 wherein R is methyl.
 52. A compound according to claim 45wherein R is methyl.
 53. A compound according to claim 2 wherein R ismethyl.
 54. A halogen-containing polymer composition containing acompound according to claim 1 in an amount effective to heat stabilizethe polymer.
 55. A composition according to claim 54 wherein the halogencontaining polymer is selected from the group consisting of vinylchloride polymers, chlorinated polyethylene, chlorinated rubber,chlorinated polystyrene, chlorinated polyvinyl chloride and rubberhydrochloride.